The present invention relates to an enolate functionalised reaction intermediate, a method for its preparation and a vinylic polymer produced from reaction of said enolate functionalised reaction intermediate with vinylic monomer. Living or immortal polymerisation is a type of polymerisation that does not terminate naturally. Each initiator molecule produces one growing chain such that the polymer grows linearly with time. Therefore the degree of polymerisation can be controlled to some extent. This method has been developed by Inoue for the living polymerisation of both methacrylates and acrylates using aluminium porphyrins, of the general formula (TPP)AIX, as initiators with irradiation from a xenon arc (Polym. Prepr. Jpn. (English Edition) 1992, 41, E93(IIID-06) and E96(IIID-12). 
(TPP)AIX where X=CH3 or SCH2CH2CH3 
At ambient temperature each (TPP)AIX molecule was found to generate a polymer chain and excellent control of molecular weight was achieved.
Subsequently Inoue discovered that the further addition of a Lewis acid greatly enhances the rate of propagation. For example (TPP)AIMe initiated polymerisation of methylmethacrylate (MMA), in the presence of irradiated light, was found to yield 6.1% polymethylmethacrylate after 2.5 hours. With the addition of a Lewis acid, for example a bulky aluminium phenoxide, there was quantitative polymerisation within 3 seconds. More recently Inoue has disclosed such systems where the presence of irradiated light is not required. For example (TPP)AIX, where X=SPropyl, initiated polymerisation of MMA in the presence of a Lewis acid, where there is complete monomer conversion after 1.5 minutes at 80xc2x0 C. (T. Kodeira and K. Mori, Makromol. Chem. Rapid Commun. 1990, 11, 645). However the molecular weights that have been produced with this system have been low, for example 22,000.
It is reported, by Inoue, that the initial reaction is of the (TPP)AIX complex with monomer to form an enolate initiator as the reaction intermediate, in the presence of irradiated light. This enolate can then react with further monomer in the presence of the Lewis acid to develop the polymer chain.
It is an object of the present invention to provide an enolate functionalised reaction intermediate, a method for its preparation and a vinylic polymer produced from reaction of said enolate functionalised reaction intermediate with vinylic monomer.
Accordingly in a first aspect the present invention provides an enolate functionalised reaction intermediate of general formula (I) 
wherein X is an alkyl group; Z is selected from the group consisting of alkyl, hydrogen, halogen, alkoxy, thiol, aryloxy or ester; n is an integer and includes n=0; Y is alkyl or H; the tetradentate ligand around the Al is optionally substituted
In a second aspect, the present invention provides a process for the preparation of an enolate functionalised reaction intermediate of general formula (I) wherein X is an alkyl group; Z is selected from the group consisting of alkyl, hydrogen, halogen, alkoxy, thiol, aryloxy or ester; n is an integer and includes n=0; Y is alkyl or H, the tetradentate ligand around the Al is optionally substituted which process comprises the steps of
(i) Preparing a metal complex of general formula (II), 
where R is a leaving group, in a solvent
(ii) Preparing a metal enolate of a monomer, selected from the group consisting of (alk)acrylic acids or alkyl esters thereof, in a second solvent
(iii) Mixing the two solutions of (i) and (ii) together
(iv) Isolating the enolate functionalised reaction intermediate
In a third aspect the present invention provides a vinylic polymer which is prepared from the reaction of an enolate functionalised reaction intermediate of general formula (I) with a vinylic monomer and a Lewis acid of general formula (III) 
wherein at least one of C, D or E is capable of forming a coordination bond with Al of the enolate functionalised reaction intermediate, the others of C, D or E are bulky groups and M is selected from the group consisting of aluminium, magnesium, zinc and boron.
In the enolate functionalised reaction intermediate (I) X is preferably an alkyl group ranging from C1-C20. For Z by thiol we mean both SH and SR1 groupings where R1 includes alkyl, ester, ether. Z is preferably alkyl or hydrogen. Where Z may be alkyl it is preferably C1-C8 alkyl, more preferably methyl. n is preferably in the range 1 to 10, more preferably 1 to 5. When Y is an alkyl group it is preferably C1-C20, more preferably C1-C4. Optional substitution is preferably on the two aromatic rings of the tetradentate ligand around Al, more preferably substitution is of two tertiary butyl groups on each of these two aromatic rings.
In the process of the present invention the metal complex is of a general formula (II) where R is preferably chosen from the group consisting of alkyl, halogen, alkoxy, thiol, aryloxy or ester. The tetradentate ligand around the Al may be optionally substituted. Optional substitution is preferably on the two aromatic rings of the tetradentate ligand around the Al, more preferably the substitution is of two tertiary butyl groups on each of these two aromatic rings. Preferably the ratio of number of moles of metal complex (II) to moles of the metal enolate of a monomer, selected from the group consisting of (alk)acrylic acids or alkyl esters thereof is 1:1.
In the third aspect of the invention the bulky groupings in the Lewis acid (III) are preferably the same, in particular phenoxide or a substituted phenoxide or thiolate; The one of C, D or E which is capable of forming a co-ordination bond with the Al of the enolate functionalised reaction intermediate is preferably chosen from the group consisting of alkyl, halogen, alkoxy, aryloxy and ester, more preferably it is an alkyl group and more specifically methyl. M is preferably aluminium.
The vinylic polymers that can be produced according to this invention include homo and copolymers of the corresponding vinylic monomers such as alkyl (alk)acrylic acid and esters thereof, functionalised alkyl(alk)acrylic acid and esters thereof, for example hydroxy, halogen, amine functionalised, styrene, vinyl acetates, butadiene, olefins or olefinic oxides. By (alk)acrylic, we mean that either the alkacrylic or the analogous acrylic may be used. For both homo and copolymers the monomers are preferably alkyl (alk)acrylic acid and esters thereof, more preferably alkyl(meth)acrylates. These polymerisations can be conducted in such a way that architectural copolymers, for example block, ABA and stars, can be produced.
For both homo and copolymers the monomers are preferably alkyl (meth)acrylates. The ratio of number of moles of vinylic monomer to moles of enolate functionalised reaction intermediate is preferably from 1:1 to 20000:1. The ratio of the number of moles of enolate functionalised reaction intermediate to number of moles of Lewis acid preferably ranges from 1:0.1 to 1:100, more preferably from 1:0.2 to 1:10.
Polymerisation can be undertaken in the presence of a solvent, for example toluene, dichloromethane and tetrahydrofuran, or in the bulk monomer. The polymerisation is preferably undertaken at between xe2x88x92100 and 150xc2x0 C., more preferably between xe2x88x9250 and 50xc2x0 C., in particular between 15 to 40xc2x0 C. The present invention is illustrated by reference to the following examples.